Crystal morphology-dependent graft polymerization in poly(ether ether ketone) films
Crystal morphology-dependent graft polymerization in poly(ether ether ketone) films
复制标题
聚醚醚酮薄膜中晶体形态依赖的接枝聚合
DOI：
10.1016/j.polymer.2013.04.007
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发表时间：
2013
期刊：
影响因子：
4.6
通讯作者：
Y. Maekawa
中科院分区：
文献类型：
--
作者：
S. Hasegawa;S. Takahashi;H. Iwase;S. Koizumi;M. Ohnuma;Y. Maekawa
研究了苯乙烯磺酸乙酯（E4 S）在聚醚醚酮（PEEK）薄膜上辐射接枝聚合的结晶度和片层结构等晶体形态对接枝聚合反应的影响。用30-150 kGy辐照具有11 - 32%堆叠度的PEEK膜，并在80 °C下在E4 S/1，4-二氧六环溶液中进行接枝聚合。对于堆叠度在11%和26%之间的PEEK膜，接枝聚合进行并达到高达70%的接枝度，而对于堆叠度高于26%的那些，反应几乎不进行。引发辐照PEEK膜中接枝聚合的苯氧基自由基的浓度在整个结晶度范围内（11-32%）是恒定的。另一方面，在小角X射线散射（SAXS）曲线中，在结晶度约为26%时，观察到Q = 0.44 nm−1（对应于14 nm的片层间距）处的峰强度的不连续变化;即，堆叠度大于26%的PEEK膜在拉伸方向上表现出显著的各向异性散射。从上述结果判断，可以得出结论，苯乙烯衍生物到PEEK膜上的接枝聚合受到抑制单体扩散到膜中的定向层状结构的形成的影响。
The effect of crystal morphology, such as the crystallinity and lamellar structure, on the radiation-induced graft polymerization of styrenesulfonate ethyl ester (E4S) onto poly(ether ether ketone) PEEK films was evaluated. The PEEK films possessing crystallinities ranging from 11 to 32% were irradiated with 30–150 kGy, and the graft polymerization was performed in an E4S/1,4-dioxane solution at 80 °C. For the PEEK films with crystallinities between 11 and 26%, the graft polymerization proceeded and reached grafting degrees of up to 70%, whereas for those having crystallinities higher than 26%, the reaction barely proceeded. The concentration of phenoxy radicals that initiated the graft polymerization in the irradiated PEEK films was constant over the entire range of crystallinity (11–32%). On the other hand, in the small-angle X-ray scattering (SAXS) profiles, a discontinuous change in the peak intensity at Q = 0.44 nm−1, which corresponds to a lamellar spacing of 14 nm, was observed at a crystallinity of approximately 26%; namely, the PEEK films with a crystallinities greater than 26% exhibited prominent anisotropic scattering in the drawing direction. Judging from the above results, it can be concluded that the graft polymerization of styrene derivatives onto the PEEK films was affected by the formation of oriented lamellar structures that inhibited monomer diffusion into the films.